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Abstract Calcium dicarbide, CaC₂, has been characterized at high resolution in the laboratory, and its main isotopologue,⁴⁰CaC₂, has been assigned to 14 rotational emission lines between 14 and 115 GHz, including 12 previously unassigned lines, in the expanding molecular envelope of the evolved carbon star IRC+10216. Aided by high-level quantum calculations and measurements of multiple isotopologues, CaC₂is determined to be a T-shaped molecule with a highly ionic bond linking the metal atom to the C₂unit, very similar in structure to isovalent magnesium dicarbide (MgC₂). The excitation of CaC₂is characterized by a very low rotational temperature of 5.8 ± 0.6 K and a kinetic temperature of 36 ± 16 K, similar to values derived for MgC₂. On the assumption that the emission originates from a 30″ shell in IRC+10216, the column density of CaC₂is (5.6 ± 1.7) × 10¹¹cm⁻². CaC₂is only the second Ca-bearing molecule besides CaNC and only the second metal dicarbide besides MgC₂identified in space. Owing to the similarity between the predicted ion–molecule chemistry of Ca and Mg, a comparison of the CaC₂abundance with that of MgC₂and related species permits empirical inferences about the radiative association–dissociative recombination processes postulated to yield metal-bearing molecules in IRC+10216 and similar objects. 

Abstract We report the detection of magnesium dicarbide, MgC₂, in the laboratory at centimeter wavelengths and assign²⁴MgC₂,²⁵MgC₂, and²⁶MgC₂to 14 unidentified lines in the radio spectrum of the circumstellar envelope of the evolved carbon star IRC+10216. The structure of MgC₂is found to be T-shaped with a highly ionic bond between the metal atom and the C₂unit, analogous to other dicarbides containing electropositive elements. A two-temperature excitation model of the MgC₂emission lines observed in IRC+10216 yields a very low rotational temperature of 6 ± 1 K, a kinetic temperature of 22 ± 13 K, and a column density of (1.0 ± 0.3) × 10¹²cm⁻². The abundance of MgC₂relative to the magnesium–carbon chains MgCCH, MgC₄H, and MgC₆H is 1:2:22:20 and provides a new constraint on the sequential radiative association–dissociative recombination mechanisms implicated in the production of metal-bearing molecules in circumstellar environments. 

New sources of parity and time-reversal violation are predicted by well motivated extensions of the Standard Model and can be effectively probed by precision spectroscopy of atoms and molecules. Chiral molecules have distinguished enantiomers which are related by parity transformation. Thus they are promising candidates to search for parity violation at molecular scales, which has yet to be observed. In this work, we show that precision spectroscopy of the hyperfine structure of chiral molecules is sensitive to new physics sources of parity and time-reversal violation. In particular, such a study can be sensitive to regions unexplored by terrestrial experiments of a new chiral spin-1 particle that couples to nucleons. We explore the potential to hunt for time-reversal violation in chiral molecules and show that it can be a complementary measurement to other probes. We assess the feasibility of such hyperfine metrology and project the sensitivity in ${\text{CHDBrI}}^{+}$. Published by the American Physical Society2024 

We report the hyperfine-resolved rotational spectrum of the gas-phase phenoxy radical in the 8−25 GHz frequency range using cavity Fourier transform microwave spectroscopy. A complete assignment of its complex but well-resolved fine and hyperfine splittings yielded a precisely determined set of rotational constants, spin-rotation parameters, and nuclear hyperfine coupling constants. These results are interpreted with support from high-level quantum chemical calculations to gain detailed insight into the distribution of the unpaired π electron in this prototypical resonance-stabilized radical. The accurate laboratory rest frequencies enable studies of the chemistry of phenoxy in both the laboratory and space. The prospects of extending the present experimental and theoretical techniques to investigate the rotational spectra of isotopic variants and structural isomers of phenoxy and other important gas-phase radical intermediates that are yet undetected at radio wavelengths are discussed. 

Recent advances in circumstellar metal chemistry and laser-coolable molecules have spurred interest in the spectroscopy and electronic properties of alkaline earth metal-bearing polyatomic molecules. We report the microwave rotational spectra of two members of this important chemical family, the linear magnesium- carbon chains MgC4H and MgC3N, detected with cavity Fourier transform microwave spectroscopy of a laser ablation-electric discharge expansion. The rotation, fine, and hyperfine parameters have been derived from the precise laboratory rest frequencies. These experimental results, combined with a theoretical quantum chemical analysis, confirm the recent identification of MgC4H and MgC3N in the circumstellar envelope of the evolved carbon-rich star IRC+10216. The spectroscopic data also provide insight into the structural and electronic properties that influence the metal-based optical cycling center in this unique class of laser-coolable polyatomics. 

Large-amplitude vibrational motion influences the rovibrational structure of molecules that tunnel between multiple wells. Reaction path (RP) Hamiltonians, and curvilinear coordinates more gen- erally, are useful for modelling pure vibrational motion in these systems and provide a practical framework for calculating accurate ab initio anharmonic vibrational energies and tunnelling split- tings with perturbation theory. These computational tools also offer the means to address rotation- vibration coupling associated with large-amplitude motion in rotating molecules. In this paper, we incorporate the reduced axis system (RAS) frameembeddingwithRPHamiltoniansandsecond-order vibrational Møller-Plesset perturbation theory (VMP2). Because the RP-RAS Hamiltonian eliminates rotation-vibration momentumcoupling everywhere along a one-dimensional reaction path, it is well suited for rovibrational VMP2 methods, the convergence of which relies critically on approximate vibration-vibration and vibration-rotation separability. The accuracy of this combined RP-RAS-VMP2 scheme is demonstrated by comparisons with numerically exact variational calculations and VMP2 parameters based on traditional Eckart embeddings for reduced-dimension models of torsional tunnelling in hydrogenperoxideandinversion tunnelling in cyclopropyl radical. Thefavourablecom- putational scaling ofVMP2makes it a promising strategy for calculating accurate tunnelling-rotation parameters for medium-sized and larger molecules in full dimensionality. 

Context.The methyl cation (CH₃⁺) has recently been discovered in the interstellar medium through the detection of 7 μm (1400 cm⁻¹) features toward the d203-506 protoplanetary disk by the JWST. Line-by-line spectroscopic assignments of these features, however, were unsuccessful due to complex intramolecular perturbations preventing a determination of the excitation and abundance of the species in that source. Aims.Comprehensive rovibrational assignments guided by theoretical and experimental laboratory techniques provide insight into the excitation mechanisms and chemistry of CH₃⁺in d203-506. Methods.The rovibrational structure of CH₃⁺was studied theoretically by a combination of coupled-cluster electronic structure theory and (quasi-)variational nuclear motion calculations. Two experimental techniques were used to confirm the rovibrational structure of CH₃⁺:(1) infrared leak-out spectroscopy of the methyl cation, and (2) rotationally resolved photoelectron spectroscopy of the methyl radical (CH₃). In (1), CH₃⁺ions, produced by the electron impact dissociative ionization of methane, were injected into a 22-pole ion trap where they were probed by the pulses of infrared radiation from the FELIX free electron laser. In (2), neutral CH₃, produced by CH₃NO₂pyrolysis in a molecular beam, was probed by pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy. Results.The quantum chemical calculations performed in this study have enabled a comprehensive spectroscopic assignment of thev₂⁺andv₄⁺bands of CH₃⁺detected by the JWST. The resulting spectroscopic constants and derived EinsteinAcoefficients fully reproduce both the infrared and photoelectron spectra and permit the rotational temperature of CH₃⁺(T= 660 ± 80 K) in d203-506 to be derived. A beam-averaged column density of CH₃⁺in this protoplanetary disk is also estimated. 

The unique optical cycling efficiency of alkaline earth metal–ligand molecules has enabled significant advances in polyatomic laser cooling and trapping. Rotational spectroscopy is an ideal tool for probing the molecular properties that underpin optical cycling, thereby elucidating the design principles for expanding the chemical diversity and scope of these platforms for quantum science. We present a comprehensive study of the structure and electronic properties in alkaline earth metal acetylides with high-resolution microwave spectra of 17 isotopologues of MgCCH, CaCCH, and SrCCH in their²Σ⁺ground electronic states. The precise semiexperimental equilibrium geometry of each species has been derived by correcting the measured rotational constants for electronic and zero-point vibrational contributions calculated with high-level quantum chemistry methods. The well-resolved hyperfine structure associated with the^1,2H,¹³C, and metal nuclear spins provides further information on the distribution and hybridization of the metal-centered, optically active unpaired electron. Together, these measurements allow us to correlate trends in chemical bonding and structure with the electronic properties that promote efficient optical cycling essential to next-generation experiments in precision measurement and quantum control of complex polyatomic molecules.